Method for producing ceramic product with anti-counterfeiting function by using high-temperature-resistant upconversion material
By using upconversion materials doped with Yb3+ and Er3+ ions in a YSZ matrix, the problem of decreased luminescence performance of ceramic products under high temperature conditions was solved, realizing the concealed tracing and identification functions of ancient ceramics.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- JINGDEZHEN GUOXI PORCELAIN CO LTD
- Filing Date
- 2026-01-26
- Publication Date
- 2026-05-01
AI Technical Summary
The lack of upconversion materials in existing technologies that are suitable for high-temperature ceramic processes and possess both concealment and stability makes it difficult for replicas of ancient ceramics to maintain their luminescence properties and distinctiveness under high-temperature conditions.
High-temperature upconversion materials based on YSZ, doped with Yb3+ and Er3+ ions, are prepared by co-precipitation and combined with ceramic underglaze or overglaze pigments. After high-temperature sintering, they still maintain stable upconversion luminescence properties.
Under 980 nm infrared laser excitation, ceramic products exhibit visible light at the upconversion material location, realizing the concealed tracing and identification function of ancient ceramics, which is suitable for high-temperature ceramic preparation processes.
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Figure CN121949006A_ABST
Abstract
Description
A method for producing anti-counterfeiting ceramic products using high-temperature resistant upconversion materials Technical Field
[0001] This invention relates to the field of ceramic technology, and in particular to a method for producing ceramic products with anti-counterfeiting functions using high-temperature resistant upconversion materials. Background Technology
[0002] With the continuous advancement of modern technology, the techniques for imitating ancient ceramics have become increasingly sophisticated, with some imitations reaching the level of "scientific forgery." Currently, commonly used methods for scientifically identifying ancient ceramics include thermoluminescence, neutron activation analysis (NAA), laser-induced breakdown spectroscopy (LIBS), and proton-excited X-ray fluorescence analysis (PIXE). However, imitators can now interfere with these scientific testing methods by artificially adding radioactive elements and performing reverse analysis and ratio adjustments to the original composition, leading to deviations in authentication. This problem not only affects the order of the contemporary art market but may also cause confusion for future research, necessitating the introduction of identifiable and traceable technologies into the replication process.
[0003] The purpose of replicating ancient ceramics is to inherit the essence of ancient craftsmanship and art, and to reproduce their original form, material characteristics, and cultural information. An ideal replica should possess a high degree of fidelity while also having identifiable modern markings to avoid being mistaken for an authentic antique in the future. Therefore, developing a replication technology with stable traceability has become an important issue in this field.
[0004] Currently, common tracer materials fall into two main categories: organic and inorganic. Organic fluorescent materials are prone to decay over time and have poor stability, making them unsuitable for replicating ceramic artifacts that require long-term preservation. Conventional inorganic tracer materials are mostly based on the principle of down-conversion photoluminescence, such as luminescent pigments or ultraviolet-excited materials. Their emission wavelengths are mostly within the visible light range, making them easily identifiable by the human eye and failing to meet the concealment requirements of ancient ceramic replicas.
[0005] Anti-Stokes luminescent materials, also known as up-conversion photoluminescence materials, can emit short-wavelength visible light when excited by long-wavelength light (such as infrared light), exhibiting high concealment and anti-interference capabilities. These materials are typically inorganic solid compounds doped with rare-earth elements, utilizing the metastable energy levels of rare-earth ions to achieve a multiphoton superposition luminescence mechanism. Although upconversion materials have been widely used in fields such as biomarking, anti-counterfeiting, and optical devices, research on their stability under high-temperature conditions and compatibility with ceramic processes remains relatively lacking.
[0006] Of particular note is that traditional upconversion materials are prone to structural changes and thermal quenching after high-temperature secondary sintering, leading to a significant decrease or even loss of luminescent properties. Furthermore, the high-temperature environment during ceramic preparation and the complex physicochemical reactions between glazes and additives may further alter the crystal structure and optical properties of the material. Therefore, developing a material that can withstand the firing temperature of ceramics while maintaining stable upconversion luminescence properties is of great value for achieving covert tracing and future identifiability in the replication of ancient ceramics; however, no relevant technologies have been reported to date.
[0007] In summary, the existing technology lacks an upconversion material that is suitable for high-temperature ceramic processes and possesses both concealment and stability, which is the key technical problem that this invention aims to solve. Summary of the Invention
[0008] The main objective of this invention is to propose a method for producing anti-counterfeiting ceramic products using high-temperature resistant (≥1100℃) upconversion materials, in order to solve the above-mentioned technical problems.
[0009] To achieve the above objectives, this invention proposes a method for producing anti-counterfeiting ceramic products using a high-temperature resistant upconversion material: A high-temperature resistant upconversion material is added externally to underglaze pigments, the amount of which is 3-5 wt% of the total weight of the underglaze pigments; patterns are drawn on the ceramic body using the underglaze pigments with the added high-temperature resistant upconversion material; a transparent glaze is applied; and the ceramic product with anti-counterfeiting function is obtained by firing at 1100-1320 °C; or, a slurry A is coated on the surface of the ceramic body; then slurry B is partially covered; and the ceramic product with anti-counterfeiting function is obtained by firing at 690-820 °C; slurry A includes lead-free glass powder and a modifier; slurry B includes decorative pigments, a modifier, and the high-temperature resistant upconversion material; the amount of which is 1-5 wt% of the total weight of slurry B; wherein the high-temperature resistant upconversion material is: YSZ: x mol% Er 3+ , y mol% Yb 3+ ;0 < x ≤ 6, 0 < y ≤ 20.
[0010] This invention incorporates a high-temperature resistant upconversion material into ceramic glaze, combining it with traditional processes to prepare ceramic products. Even after secondary sintering, the high-temperature resistant upconversion material retains stable luminescent properties. This high-temperature resistant upconversion material uses yttrium-stabilized zirconium oxide (YSZ) as a matrix and is doped with sensitizer ions Yb. 3+ and activator ions Er 3+ Yb was obtained 3+ / Er 3+YSZ-co-doped materials possess stable physical and chemical properties and achieve upconversion luminescence under 980 nm infrared laser excitation, converting invisible infrared excitation light into visible light emission, emitting green or red light. This material can be applied in high-temperature ceramic manufacturing processes, retaining its high-efficiency luminescence performance even after secondary high-temperature sintering. The fired ceramic products exhibit infrared excitation luminescence characteristics at the locations coated with this high-temperature resistant upconversion material, showing broad application prospects in the field of ceramic tracer and counterfeit detection technology.
[0011] Preferably, x is 2 to 4 and y is 10 to 18.
[0012] Preferably, x is 2 or 4, and y is 18.
[0013] Preferably, the upconversion material has a main emission peak of 540 nm or 660 nm when excited by a 980 nm infrared laser.
[0014] Preferably, the blending agent is a mixture of frankincense oil and camphor oil, wherein the volume ratio of frankincense oil to camphor oil is 80:20.
[0015] Preferably, the preparation method of the high-temperature resistant upconversion material includes the following steps: S1, dissolving zirconium source, yttrium source, ytterbium source, and erbium source in deionized water and stirring until completely dissolved; S2, adding the yttrium-containing solution, ytterbium-containing solution, and erbium-containing solution to the zirconium-containing solution and stirring evenly to obtain a mixed solution, adding ammonia dropwise to the mixed solution until the pH value is 9-10, and heating in a water bath at 85-95 °C for 0.5-1 h to obtain a precursor solution; S3, after centrifugation, washing, and drying, calcining the precursor solution to obtain the high-temperature resistant upconversion material.
[0016] Preferably, the zirconium source is zirconium oxychloride octahydrate; the yttrium source is yttrium(III) chloride hexahydrate; the ytterbium source is ytterbium(III) chloride hexahydrate; and the erbium source is erbium acetate tetrahydrate.
[0017] Preferably, in step S3, the drying conditions are: drying at 100~120 °C to constant weight.
[0018] Preferably, in step S3, the calcination process is segmented calcination: first, the temperature is raised to 600 ℃ at a heating rate of 10~20 ℃ / min and held for 1 h; then, the temperature is raised to 1050~1250 ℃ at a heating rate of 5~10 ℃ / min and held for 0.5~4 h.
[0019] This invention prepares Yb by co-precipitation of rare earth ions and matrix components in solution. 3+ / Er 3+YSZ co-doped material. Rare earth chlorides are dissolved and mixed, and ammonia is slowly added dropwise while adjusting the pH value to form a precursor precipitate. After centrifugation, washing, drying, and calcination, the precipitate is obtained. The co-precipitation method used in this invention is simple to operate and low in cost. By optimizing the ion concentration and precipitation rate, heterogeneous nucleation is avoided, ultimately yielding stable and high-quality Yb. 3+ / Er 3+ YSZ co-doped materials.
[0020] Compared to existing technologies, the high-temperature resistant upconversion material used in this invention retains its properties and maintains high-efficiency luminescence performance even after high-temperature secondary sintering. Furthermore, it exhibits excellent adhesion to the ceramic glaze. After firing, the painted areas with the added upconversion material emit visible light under 980nm infrared laser excitation, enabling ceramic traceability and counterfeit detection. Attached Figure Description
[0021] To more clearly illustrate the technical solutions in the embodiments of this application or the prior art, the drawings used in the description of the embodiments or the prior art will be briefly introduced below. Obviously, the drawings described below are only some embodiments of this application. For those skilled in the art, other related drawings can be obtained based on these drawings without creative effort.
[0022] Figure 1 is a schematic diagram of the high-temperature resistant upconversion material sample prepared in Example 4 emitting red light under 980 nm infrared laser excitation; Figure 2 is the XRD pattern of the high-temperature resistant upconversion material sample prepared in Example 4; Figure 3 is the XRD pattern of the high-temperature resistant upconversion material sample prepared in Example 8; Figure 4 is the standard diffraction peak data diagram of yttrium oxide stabilized zirconia (YSZ); Figure 5 is a schematic diagram of partial luminescence of the high-temperature resistant upconversion material of Example 9 after baking on the ceramic surface; Figure 6 is a comparison diagram of luminescence of ceramic products prepared in Example 10-1; Figure 7 is a comparison diagram of luminescence of ceramic products prepared in Example 10-2; Figure 8 is a comparison diagram of luminescence of ceramic products prepared in Example 11.
[0023] The realization of the purpose, functional features and advantages of this application will be further explained in conjunction with the embodiments and with reference to the accompanying drawings. Detailed Implementation
[0024] The technical solutions in the embodiments of the present invention will be clearly and completely described below. Obviously, the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention. It should be noted that, in the absence of conflict, the embodiments and features in the embodiments of this application can be combined with each other. At the same time, the raw materials mentioned below, unless otherwise specified, are all commercially available products; the process steps or preparation methods not mentioned in detail are all process steps or preparation methods known to those skilled in the art.
[0025] This invention proposes a method for producing anti-counterfeiting ceramic products using a high-temperature resistant upconversion material: A high-temperature resistant upconversion material is added externally to underglaze pigments, the amount of which is 3-5 wt% of the total weight of the underglaze pigments; patterns are drawn on the ceramic body using the underglaze pigments with the added high-temperature resistant upconversion material; a transparent glaze is applied; and the ceramic product with anti-counterfeiting function is obtained by firing at 1100-1320 °C; or, a slurry A is coated onto the surface of the ceramic body; then slurry B is partially covered; and the ceramic product with anti-counterfeiting function is obtained by firing at 690-820 °C; slurry A includes lead-free glass powder and a modifier; slurry B includes decorative pigments, a modifier, and the high-temperature resistant upconversion material; and the amount of the high-temperature resistant upconversion material added is 1-5 wt% of the total weight of slurry B. wt%; the blending agent is a mixture of frankincense oil and camphor oil, wherein the volume ratio of frankincense oil to camphor oil is 80:20; wherein the high-temperature resistant upconversion material is: YSZ: x mol% Er 3+ , y mol% Yb 3+ ;0 < x ≤ 6, 0 < y ≤ 20.
[0026] This invention combines high-temperature resistant upconversion materials with traditional processes, applying the materials to both underglaze and overglaze pigments in ceramics with excellent adhesion. The glaze does not cause light scattering or absorption issues for the upconversion materials. Under 980 nm infrared laser irradiation on the fired ceramic tile surface, visible light can be seen in the areas where the upconversion materials have been added. The lead-free glass powder in slurry A possesses excellent high-temperature stability and adhesion to the ceramic glaze, forming a uniform and dense adhesive layer during the firing process, ensuring the upconversion materials firmly adhere to the ceramic surface.
[0027] As is well known, the manufacturing process of ceramic products typically requires high-temperature sintering. Therefore, solidifying upconversion materials onto the ceramic surface and using infrared light as the excitation source to convert the infrared excitation light into visible light emission, thereby achieving the tracer purpose of exhibiting fluorescence under specific frequency laser irradiation, faces several significant technical bottlenecks: 1. Thermal quenching: Common upconversion materials such as NaYF4:Yb / Er experience a sharp decline in luminescence efficiency at temperatures exceeding 500℃ due to increased lattice vibrations caused by high temperatures. This leads to increased non-radiative relaxation loss of excited-state energy, inhibiting the upconversion luminescence process. 2. Matrix phase transformation failure: The matrix of most upconversion materials undergoes lattice distortion or decomposition at high temperatures. For example, the lattice structure of some fluoride matrix materials changes under high-temperature sintering conditions, resulting in the loss of optical properties and the inability to achieve the expected luminescence function. Especially in ceramic materials, new crystal phases are formed during sintering, necessitating the avoidance of mutual interference between the upconversion material and the ceramic material. 3. Poor bonding with ceramics: The upconversion material lacks effective chemical bonding or micro-mechanical interlocking with the ceramic glaze. During the high-temperature firing process, the glaze melts and flows, and during the subsequent cooling and shrinkage, the upconversion material is prone to melting or falling off the glaze.
[0028] Therefore, the present invention has successfully overcome the above-mentioned technical problems and achieved that the upconversion material still maintains high-efficiency luminescence performance after high-temperature secondary sintering.
[0029] This invention employs a yttrium-stabilized zirconia (YSZ) structure as the upconversion material matrix. The matrix serves as the carrier for the upconversion luminescent material; it does not emit light itself, but provides a suitable crystal field for the dopant ions to emit light. In existing technologies, many upconversion material matrices undergo lattice distortion or decomposition at high temperatures. For example, some fluoride matrix materials experience changes in their lattice structure during high-temperature sintering, leading to a loss of optical properties and preventing the achievement of the intended luminescent function. The YSZ used in this invention has lower phonon energy, reducing energy loss of excitation light and improving upconversion luminescence efficiency. Simultaneously, YSZ exhibits good chemical stability and is stable and compatible with ceramic materials in high-temperature environments. The activator ions, acting as luminescent centers, function to achieve upconversion luminescence through multiphoton absorption or energy transfer. This invention employs Er... 3+ As activator ions, they can emit green light (~540 nm) or red light (~660 nm) by absorbing two or more photons. The green emission pathway is: Excitation process: Absorption of 980 nm photons ( 4 I 15 / 2 → 4 F 7 / 2 ), followed by nonradiative relaxation 2 H 11 / 2 and 4 S 3 / 2 Energy level. Radiative transition:2 H 11 / 2 → 4 I 15 / 2 (Emits ~540 nm green light); 4 S 3 / 2 → 4 I 15 / 2 (Emits ~540 nm green light) (and) 2 H 11 / 2 Similar areas are usually merged into a green light band. The red light path is: cross relaxation: two adjacent Er... 3+ Ions exchange energy: Er 3+ ( 4 F 7 / 2 +Er 3+ ( 4 I 11 / 2 → 2 Er 3+ ( 4 F 9 / 2 This process transfers energy to 4 F 9 / 2 Energy level, then 4 F 9 / 2 → 4 I 15 / 2 Transition emission of ~660 nm red light. This invention uses Yb 3+ As a sensitizer ion, it absorbs excitation light and efficiently transfers energy to the activator through resonant energy transfer.
[0030] It should be noted that the doping concentrations of activator ions and sensitizer ions need to be precisely controlled. Excessive activator ion concentration can easily induce inter-ion cross-relaxation, leading to a decrease in luminescence efficiency. While a high concentration of sensitizer ions can enhance the ability to capture excitation light, it is still necessary to avoid energy transfer due to excessively close ion spacing.
[0031] In some preferred embodiments, the present invention optimizes Er 3+ and Yb 3+ The doping concentration is adjusted to ensure maximum energy transfer efficiency. Preferably, x is 2-4 and y is 10-18. More preferably, x is 2 or 4 and y is 18.
[0032] The upconversion material described in this invention, when excited by a 980 nm infrared laser, has a main emission peak at 540 nm (green light) or 660 nm (red light).
[0033] Numerous methods exist for synthesizing rare-earth upconversion luminescent materials, including hydrothermal / solvothermal methods, coprecipitation methods, sol-gel methods, and high-temperature solid-state methods, each with its own advantages and disadvantages. The commonly used high-temperature solid-state method obtains highly crystalline materials by high-temperature calcination of a mixture of rare-earth salts and a matrix precursor, suitable for bulk or micron-sized crystals. However, the resulting particles are of uneven size, and high-temperature calcination is energy-intensive, requiring subsequent ball milling for refinement. The sol-gel method utilizes the hydrolysis of metal alkoxides to form a sol, followed by gelation and calcination to obtain the material. This method can prepare high-purity materials, but its process is complex and time-consuming.
[0034] In some preferred embodiments, the preparation method of the above-mentioned high-temperature resistant upconversion material includes the following steps: S1, dissolving the zirconium source, yttrium source, ytterbium source, and erbium source in deionized water and stirring until completely dissolved; to ensure the high purity and performance stability of the material, metal salt raw materials with a purity ≥99.9% are preferred. The zirconium source is zirconium oxychloride octahydrate; the yttrium source is yttrium(III) chloride hexahydrate; the ytterbium source is ytterbium(III) chloride hexahydrate; and the erbium source is erbium acetate tetrahydrate.
[0035] S2. Add the yttrium-containing solution, ytterbium-containing solution, and erbium-containing solution to the zirconium-containing solution, stir until homogeneous, and obtain a mixed solution. Add ammonia water dropwise to the mixed solution at a rate of 1 drop / s until the pH value is 9-10. Transfer the mixed solution after adding ammonia water to a constant temperature water bath with stirring, and heat in a water bath at 85-95 ℃ for 0.5-1 h to age the precipitate and obtain the precursor solution. S3. Collect the precipitate from the precursor solution by centrifugation, and wash it with deionized water and anhydrous ethanol by centrifugation to remove Cl. - and NH4 + Ions. After drying to constant weight at 100–120 °C, a segmented calcination process is employed: first, the temperature is increased to 600 °C at a rate of 10–20 °C / min and held for 1 h; then, the temperature is increased to 1050–1250 °C at a rate of 5–10 °C / min and held for 0.5–4 h. After calcination, the material is cooled to room temperature and ground to obtain the high-temperature resistant upconversion material.
[0036] This invention prepares Yb by co-precipitation of rare earth ions and matrix components in solution. 3+ / Er 3+ YSZ co-doped material. Rare earth chlorides were dissolved and mixed, and ammonia was slowly added dropwise while adjusting the pH value to form a precursor precipitate. After centrifugation, washing, drying, and calcination, the precipitate was obtained.
[0037] It should be noted that this invention employs a special segmented calcination process to optimize the crystal structure: firstly, the temperature is raised to 600 °C at a heating rate of 10–20 °C / min and held for 1 h to decompose organic matter and residual nitrates; subsequently, the temperature is raised to 1050–1250 °C at a heating rate of 5–10 °C / min and held for 0.5–4 h to promote the formation of the YSZ cubic phase. At this temperature, Y… 3+ It can be fully dissolved in the ZrO2 lattice, suppressing high-temperature phase transitions. After calcination, the sample can be rapidly cooled to 800°C and then placed in a desiccator to further avoid the negative impact of surface hydroxylation caused by moisture absorption on luminescence properties. The co-precipitation method used in this invention is simple to operate and low in cost. By optimizing the ion concentration and precipitation rate, heterogeneous nucleation is avoided, ultimately yielding stable, high-quality Yb suitable for high-temperature secondary sintering. 3+ / Er 3+ YSZ co-doped materials.
[0038] In the method for preparing ceramic products described in this invention, the underglaze pigments, slurry A, and slurry B used can all be commercially available conventional ceramic glazes, and the decorative pigments can also be commercially available conventional ceramic colorants. Those skilled in the art can adjust the types of glazes and colorants used according to actual needs.
[0039] The following examples further illustrate the present invention in detail. It should also be understood that the following examples are only for further explanation of the present invention and should not be construed as limiting the scope of protection of the present invention. Any non-essential improvements and adjustments made by those skilled in the art based on the above description of the present invention are within the scope of protection of the present invention. The specific process parameters in the following examples are merely one example within a suitable range; that is, those skilled in the art can make appropriate selections within the range based on the description herein, and are not intended to be limited to the specific values in the examples below. Where specific conditions are not specified in the examples, conventional conditions or conditions recommended by the manufacturer shall apply.
[0040] The experimental reagents used in the following examples were: zirconium oxychloride octahydrate with a purity of 99.9% and purchased from Shanghai Aladdin Biochemical Technology Co., Ltd.; yttrium(III) chloride hexahydrate, ytterbium(III) chloride hexahydrate and erbium acetate tetrahydrate with a purity of 99.9% and purchased from Ron Reagent; ammonia water was of analytical grade and purchased from Shanghai Jiuyi Chemical Reagent Co., Ltd.; and anhydrous ethanol with a concentration of 99.7% and purchased from Anaiji Chemical.
[0041] In the following embodiments, Y is maintained 3+ The concentration is 8 mol%. Since the total number of moles of cations is 100 mol%, calculations show that in the following examples, Zr... 4+ The corresponding concentration is (100-8-xy)mol%, where x is Er. 3+The concentration of y is Yb 3+ The concentration.
[0042] Example 1 Preparation of high temperature resistant upconversion material includes the following steps: S1, Dissolve appropriate amounts of zirconium oxychloride octahydrate, yttrium(III) hexahydrate, ytterbium(III) hexahydrate, and erbium acetate tetrahydrate in deionized water according to the doping concentration in Table 1, and stir until completely dissolved.
[0043] S2. Add the yttrium-containing solution, ytterbium-containing solution, and erbium-containing solution to the zirconium-containing solution, stir until homogeneous, and obtain a mixed solution. Add ammonia water dropwise to the mixed solution at a rate of 1 drop / s until the pH value is 9-10. Transfer the mixed solution after adding ammonia water to a constant temperature water bath with stirring, and heat at 90 °C for 1 h to age the precipitate, obtaining the precursor solution. S3. Collect the precipitate from the precursor solution by centrifugation, wash it three times with deionized water, and finally wash it with anhydrous ethanol. Dry it at 110 °C for 12 h to constant weight, and use a segmented calcination process: first, raise the temperature to 600 °C at a rate of 20 °C / min and hold for 1 h; then raise the temperature to 1250 °C at a rate of 5 °C / min and hold for 4 h. After calcination, cool to room temperature, grind and refine, to obtain the high-temperature resistant upconversion material.
[0044] The difference between Examples 2-8 and Example 1 is that Yb is adjusted. 3+ Er 3+ The doping concentration, as well as the adjustment of the maximum temperature and holding time in the calcination process, are shown in Table 1.
[0045] The characteristics of the high-temperature resistant upconversion material samples prepared in Examples 1-8 and their luminescence properties under 980 nm infrared laser excitation are shown in Table 1.
[0046] Table 1 As shown in Table 1, the high-temperature resistant upconversion material prepared by this invention can emit red or green light under 980 nm infrared laser excitation. Among them, the sample prepared in Example 4 emits the most intense red light, as shown in Figure 1. The sample prepared in Example 8 emits the most intense green light.
[0047] X-ray diffraction analysis was performed on the high-temperature resistant upconversion materials prepared in Examples 4 and 8. The results are shown in Figures 2 and 3. Compared with the standard diffraction peak data of yttrium-stabilized zirconia (YSZ) in Figure 4, it can be seen that diffraction peaks matching the standard YSZ cubic phase were observed at the characteristic diffraction peak positions in both Figure 2 (Example 4) and Figure 3 (Example 8). This confirms the presence of this phase in the samples of Examples 4 and 8. The sharp diffraction peaks indicate good crystallinity and a complete crystal structure.
[0048] Example 9: The high-temperature resistant upconversion materials prepared in Examples 4-8 were mixed with water at a ratio of 2:1 (mass ratio). An appropriate amount of the mixture was applied to the surface of a white ceramic dish, dried, and then baked at 790°C. The baked ceramic dish was excited with 980nm infrared light; the corresponding positions in Examples 4-8 showed good luminescence. Figure 5 shows the luminescence of the upconversion materials prepared in Examples 5 (left side red light) and Example 6 (right side green light) after baking on the ceramic surface. This demonstrates that the high-temperature resistant upconversion material prepared in this invention, when coated on the ceramic tile surface, still possesses good luminescence properties after high-temperature baking.
[0049] Example 10: A method for producing anti-counterfeiting ceramic products using high-temperature resistant upconversion material, comprising the following steps: mixing the high-temperature resistant upconversion material obtained in Example 8 with modern cobalt blue pigment according to the addition ratio in Table 2; applying the mixed glaze to the ceramic body; drying and then applying a transparent glaze; firing at 1250℃ to obtain anti-counterfeiting ceramic products. Both the modern cobalt blue pigment and the transparent glaze can be commercially available ceramic glazes. In this example, the modern cobalt blue pigment used is Jingdezhen Peiyintang Kangqian No. 1, and the transparent glaze used is Jingdezhen Huacai glaze 1103 transparent glaze.
[0050] Table 2 The ceramic products prepared in Examples 10-1 and 10-2 were irradiated with a 980 nm infrared laser. The blue-and-white patterns emitted green light. The green light in Example 10-1 was weaker, as shown in Figure 6. The green light in Example 10-2 was brighter, as shown in Figure 7.
[0051] It should be noted that, after testing, the maximum firing temperature of the upconversion material described in this invention when applied to ceramic glazes after high-temperature secondary sintering is 1320℃. Therefore, combined with conventional ceramic firing processes, the upconversion material described in this invention can be applied in a firing temperature range of 1100~1320℃.
[0052] Example 11 A method for producing anti-counterfeiting ceramic products using high-temperature resistant upconversion material, comprising the following steps: mixing the high-temperature resistant upconversion material obtained in Example 4 (accounting for 5 wt% of the total weight of slurry B) with decorative pigment (accounting for 3 wt% of the total weight of slurry B) and a modifier (accounting for 4 wt% of the total weight of slurry B) to prepare slurry B, wherein the decorative pigment is a commercially available ceramic pigment that can be used as an overglaze color, and the modifier is frankincense oil and camphor oil mixed in a volume ratio of 80:20.
[0053] A slurry A is applied to the surface of a ceramic body. Slurry A comprises 10 wt% lead-free glass powder and 4 wt% modifier. After drawing the desired pattern with overglaze enamel prepared with decorative pigments, a corner of the pattern is filled with slurry B. After drying, the ceramic body is fired at 790°C to obtain a ceramic product with anti-counterfeiting features. The remaining components of slurry A and slurry B can be conventional basic slurries in the art. In this embodiment, the remaining components of slurry A and slurry B are commercially available glass white pigments from Jingdezhen Ma'anshan Ceramic Raw Materials Business Department.
[0054] The fired ceramic product was irradiated with a 980 nm infrared laser, and red light was emitted at the local position of the drawn pattern (the filling slurry B), as shown in Figure 8.
[0055] It should be noted that, after testing, the upconversion materials described in this application are all applicable to conventional baking processes, and therefore are suitable for firing temperatures in the range of 690~820℃.
[0056] In summary, this invention combines high-temperature resistant upconversion materials with traditional ceramic processes. The high-temperature resistant upconversion materials can be sintered at high temperatures twice without being affected by glazes. After firing, they have good luminescence effects and emit red or green light under 980 nm infrared laser excitation, which can realize functions such as traceability and anti-counterfeiting of ceramic products.
[0057] The above description is merely a preferred embodiment of the present invention and does not limit the patent scope of the present invention. Any equivalent structural transformations made using the contents of the present invention under the inventive concept of the present invention, or direct / indirect applications in other related technical fields, are included within the patent protection scope of the present invention.
Claims
1. A method for producing anti-counterfeiting ceramic products using high-temperature resistant upconversion materials, characterized in that, A high-temperature resistant upconversion material is added to the underglaze pigment, and the amount of the high-temperature resistant upconversion material added is 3 to 5 wt% of the total weight of the underglaze pigment; patterns are drawn on the ceramic body using the underglaze pigment with the added high-temperature resistant upconversion material. Apply a transparent glaze; fire at 1100~1320 ℃ to obtain the ceramic product with anti-counterfeiting function; or, coat the surface of the ceramic body with slurry A; Then, partially cover with slurry B; fire at 690~820 ℃ to obtain the ceramic product with anti-counterfeiting function; slurry A includes lead-free glass powder and a modifier; slurry B includes decorative pigments, a modifier, and a high-temperature resistant upconversion material; the amount of the high-temperature resistant upconversion material added is 1~5 wt% of the total weight of slurry B; wherein, the high-temperature resistant upconversion material is: YSZ: x mol% Er 3+ , y mol% Yb 3+ ;0 < x ≤ 6, 0 < y ≤ 20.
2. The method for producing anti-counterfeiting ceramic products using high-temperature resistant upconversion materials according to claim 1, characterized in that, The x is 2~4 and the y is 10~18.
3. The method for producing anti-counterfeiting ceramic products using high-temperature resistant upconversion materials according to claim 1, characterized in that, The x is 2 or 4, and the y is 18.
4. A method for producing anti-counterfeiting ceramic products using high-temperature resistant upconversion materials according to claim 1, characterized in that, The blending agent is a mixture of frankincense oil and camphor oil, wherein the volume ratio of frankincense oil to camphor oil is 80:
20.
5. A method for producing anti-counterfeiting ceramic products using high-temperature resistant upconversion materials according to claim 1, characterized in that, The preparation method of the high-temperature resistant upconversion material includes the following steps: S1, dissolving zirconium source, yttrium source, ytterbium source and erbium source in deionized water and stirring until completely dissolved; S2, adding the yttrium-containing solution, ytterbium-containing solution and erbium-containing solution to the zirconium-containing solution and stirring evenly to obtain a mixed solution, adding ammonia water dropwise to the mixed solution until the pH value is 9~10, and heating in a water bath at 85~95 ℃ for 0.5~1 h to obtain a precursor solution; S3. After centrifugation, washing and drying, the precursor solution is calcined to obtain the high-temperature resistant upconversion material.
6. A method for producing anti-counterfeiting ceramic products using high-temperature resistant upconversion materials according to claim 5, characterized in that, The zirconium source is zirconium oxychloride octahydrate; the yttrium source is yttrium(III) chloride hexahydrate; the ytterbium source is ytterbium(III) chloride hexahydrate; and the erbium source is erbium acetate tetrahydrate.
7. A method for producing anti-counterfeiting ceramic products using high-temperature resistant upconversion materials according to claim 5, characterized in that, In step S3, the drying conditions are: drying at 100~120 ℃ to constant weight.
8. A method for producing anti-counterfeiting ceramic products using high-temperature resistant upconversion materials according to claim 5, characterized in that, In step S3, the calcination process is segmented calcination: first, the temperature is raised to 600 ℃ at a heating rate of 10~20 ℃ / min and held for 1 h; then, the temperature is raised to 1050~1250 ℃ at a heating rate of 5~10 ℃ / min and held for 0.5~4 h.